Method of preparing a. mineral binder



A U i) 6D Patented Dec. 7, 1948 METHOD OF lfRE Herbe PARING A IMINE INDER ger, Washington, D. C.

No Drawing. Application December 10, 1941, Serial No. 422,460

This invention relates to mineral binder compositions and more particularly to binders comprising phosphatic or arsenious materials.

The use of phosphatic materials in the field of mineral binders has been contemplated for many years. The' principal compositions employed in the past have consisted of either phosphoric acid or solutions of certain metallic phosphates iwid. These compositions ave proved to be unsatisfactory in many respects. The binding methods employed phosphoric acid alone depend entirely upon a reaction between the acid and the material being bonded for the formation of the binder. This method is ordinarily used in binding oxides, hydroxides, a basic phosphate or silicate and finds its most frequent application in the formation of dental cements, rammed furnace linings and refractories as well as in the binding of adsorbent articles from finely divided waste bauxite. The phosphoric acid reacts with the basic material for example, aluminium hydrate, forming aluminum phosphate. In most cases there is a large excess of the hydrate present. but usually chemical hardening and the formation of insoluble oxy-phosphates proceeds slowly, unless heat is applied.

The second type ofmr previously employed comprises a solution of a phosphate of aluminum, iron, zinc m m a al in pi'iosp oric acid.

1 Claim. (Cl. 106-85) drolysis of the aluminum phosphate. A certain amount of clear solution was obtained and an attempt was made to concentrate it by heating slowly at temperatures around 80 C. However,

an ence are unfit for many purposes. In order to set and render them insoluble it is necessary tha-base,inwhlchres 1: they are similar to the p osporic acid Bi'rjders discussed above. The setting process in thiscase is even slower than in the case when phosphoric acid alone is used which may be due to the elimination of the initial intensive reaction from the mixture.

The phosphoric acid solutions of metal oxides are stable at room temperature and in certain instances remain in a liquid state even though the requisite amount of base in granular form is present for the purpose of neutralizing the acid. The application of heat, however. precipitates acid insoluble phosphates which cannot be redissolved. as. in accelerated setting processes. For example, finely divided bauxite was digested at slightly above room temperature with suiiicient phosphoric acid to form the di-basic aluminum phosphate. The'solution was dilute enough to Drevent the formation of a tacky condition and the undissolved solidswere removed therefrom by liltration in a vacuum and perforate basket centrifuge or by clarification in a solid basket centrifuge. Since the'residual solids werevery finely divided, neither of these methods was very satisfactory. A large amount of the solution was retained in the cake and unless the solution is very acid it cannot be recovered by washing due to byappreciable amounts of precipitate appeared which did not re-dissolve in the liquid. The characteristics exemplified by the foregoing procedure constitute a serious objection since they preclude the production of clear dilute acidic phosphate solutions and the concentration of these solutions by heat.

It is the principal object of this invention to provide a viscous tacky mineral binder capable of being rapidly solidified either by chemical hardening or by drying.

Another object of this invention is to provide a concentrated, clear liquid mineral binder.

Still another object of this invention is to provide a mineral binder containing phosphatic or arsenious materials and a diflerent inorganic or organic acid radical.

A further object of this invention is to provide a mineral binder containing phosphatic or arsenious materials and a different inorganic or organic acid radical capable of being rendered inactive during chemical hardening of the binder.

A still further object of this invention is to provide a mineral binder system comprising a Phosphatic or arsenious substance and a different inorganic or organic acid radical capable of being removed from the system during heating to set the binder.

This invention is primarily directed to compositions containing the PM and arsenates of trivalent metals such as aluminum, iron an nickel. Under suitableconditionscf wafer. ?9n.-

Ent. composition and inodeof productign these compositions comprising trivalent metal phosphates which may be dissolved in water to produce viscous, tacky, adhesive binders. The invention further contemplates binders obtained from a mixture of dry ingredients either by steaming the dry mixture or by utilizing the water of crystallization of the ingredients of the dry mixture to carry out the desired reaction.

ii... A

uammer 3 inite functions in the binder system and having performed that function may be rendered inactive during the chemical hardening process or eliminated from the system entirely during setting to provide a metallic phosphate or arsenate binder. The compositions of this invention and their mode of preparation fall within certain well defined groups which will now be considered specifically. V

The compositions of group are systems comprising trivalent metals a phosphate radical and an acid ra ica o a or an orga c ac dissolving a phos hate ey may e prepare y of a trivalent h c 2 rog l oric nitric or for example, takes place at temperatures of around 750 C. Thus a binder ggmposition obtained by dissolving alu um phosl hate i; smfuric acid may b calc ve o e sul- 1m a residue having the same composition as the initial aluminum phosphate from which the binder was prepared. A binder of this particular type is very acidic but may be used to advantage in cases where the final product undergoes a process of calcination.

Generally bi s of this type may be produced from bauxite, p osphoric and hydrochloric or other acids, such as for example sulfuric or nitric in place of the hydrochloric acid. Their production from aluminum chloride and phosphoric acid and aluminum phosphate and Q1- drochloric acid has proved to e 5 pie and economim presence of chloride, sulfate or nitrate ions in the form of their acids and salts, aluminum phosphate solutions are obtained which may be diluted in any proportion without hydrolysis or which after dilution may be concentrated by heating without precipitation of insoluble material.

Example 1 In one instance, bauxite was treated first with hydrochloric acid to form aluminum chloride and the dilute solution obtained was freed from insoluble suspended matter by decantation. Phosphoric acid was then added to the solution in an amount sufficient to form ortho-phosphate. The solution thus obtained was concentrated by heating and during this process the temperature rose gradually and hydrochloric acid gas is evolved and driven off. The evolution of the gas continues as the heating is continued. Sufficient acid remains in the solution to accomplish the desired result even though the heating is continued until the solution temperature rises to nearly about 150 C. If the heating is interrupted at between 125-130 C. and the solution allowed to cool, a very tacky and viscous liquid was obtained. However, when the heating was continued to nearly about 150 C., the solution upon cooling formed a hygroscopic solid which could be readily dissolved in water. without hydrolysis.

erent inorganic acid developed so far. g"?

The compositions a ng within this class are relatively neutral in character and hence are not limited in their application. These compositions comprise aqueous solutions of trivalent metal phosphates and trivale metal salts of sulfuri'c, o I I 1 n m 7 acids. Trivalent metal phosphates as for example aluminum phosphate may be dissolved in an aqueous medium along with aluminum salts of acids such as sulfuric, hydrochloric or nitric acids. The latter salts increase the solubility of aluminum phosphate.

As stated above, the phosphate of a trivalent metal may be dissolved in the presence of a soluble organic acid salt of a trivalent metal. The use of organic acid salts is limited owing to their cost and the fact that they are somewhat less effective in their action. Their principal application is in connection with binders which consist in part of organic solvents.

The setting or transformation of these compositions may be conducted by calcining as set forth in the previous group. During the calcining step the sulfate, chloride or nitrate salts of aluminum are decomposed and a residue obtained which consists of basic phosphates as distinguished from the neutral phosphates obtained by the calcining process set forth in the previous group.

Owing to the relatively neutral characteristics of this group of compositions, it is possible to transform them into solids by means of chemical hardening without employing excessive amounts of basic materials. This setting process is carried out by adding to the solution a relatively small quantity of a suitable basic substance as for example an oxide, phosphate or silicate which is capable of reacting with the binder to form an oxy-salt. The basic substance employed need not necessarily be an aluminum salt for salts of calcium, magnesium, zinc and lead may be used to effect the same result. A composition comprising an aluminum phosphate dissolved in the presence or aluminum sulfate may be reacted with a calcium or barium silicate to form an insoluble alkaline earth sulfate and a basic aluminum phosphate. Thus the sulfate radical will be rendered inactive and the composition efiectively hardened.

Example 2 The solubilizing characteristics of aluminum sulfate, chloride and nitrate are exemplified by the following procedure. One moi. or slightly less of aluminum chloride effectively dissolves one mol. of aluminum phosphate in an aqueous medium. The solution thus obtained may be heated and concentrated. Upon cooling, a viscous tacky clear solution is obtained which may be diluted with water in any proportion without spontaneous precipitation of solids due to hydrolysis. The solution may be further dehydrated by heating to above C. and if the heating is continued until the temperature of the solution increases to somewhat below C, a stable glassy solid is obtained upon cooling which may be redissolved in water.

The binders of this group may be produced from mixtures of the respective acids as for example a mixture of phosphoric and hydrochloric acids may be employed in treating a base such as aluminum hydrate or bauxite.

The compositions comprising this group are analogous to those of the preceding group in that they are relatively neutral and hence require the use of only small amounts of insolubilizing basic materials such as oxides, during chemical hardening or setting of the binder. These compositions are prepared from tdmenmetal alLgf ino anic acids such as aluminium or ferric sulfates, nltratesor chlorides and a divalent metal phosphate such as calcium pHoshates and n cised to select trivalent metal salts and divalent metal phosphates which provide ions in a liquid phase that have the ability to form complex colloidal compounds that remain as such and do not crystallize. The compositions comprising this group may be prepared either by dissolving the various ingredients in an aqueous medium or, under certain conditions, by merely mixing the dry ingredients. These binders possess all of the beneficial characteristics of those in the preced 2 method.

Example 3 One moi. of aluminum sulfate and two mols, of di-basic calcium phosphate were dissolved in an aqueous medium and heated. A viscous tacky liquid was obtained which contained a very finely divided white precipitate consistin mostly of sulphate. but which may also contain complex salts formed by the sulphate and phosphate radicals. This precipitate may be left in the binder or removed from the solution of compounds formed from alum and the phosphate and sulphate radicals such as aluminum phosphate, or sulphate or complex phosphate and sulphate salts of alum, by known methods such as deqantation. 4

The clear liquid thus obtained may be concentrated by heating without precipitation of solids owing to the presence of the sulfate ion. Upon evaporation at water bath temperatures, a glass solid is obtained which may be redissolved withou J substantial hydrolysis.

The formation of the white precipitate in the above reaction may favor the production of the tacky condition It appears, however, that the reaction of zinc phosphate and aluminum sulfate also produces tacky binders. It is, therefore, not generally true that the divalent metal ion and the sulfate ion have to be eliminated from the solution to obtain this property. It is more important that these ions in the liquid binder be capable of forming complex, colloidal type solutions which exhibit an ability to remain in this condition without crystallizing. In contrast to the binder prepared from zinc phosphate and aluminum sulfate, the reaction products of magnesium phosphate and aluminum sulfate tend to crystallize.

In the foregoing example, the aluminum sulfate and di-basic calcium phosphate were first mixed together in a dry state and then dissolved in aboutone liter of water. The solution thus obtained, while viscous and tacky was found to contain small lumps as well as to be granular. In order to overcome this objection the several Care must be exerl5 and the solutions obtained were then mixed to gether. The dkwmcium phosphate formed a slurry in water and was added to the alumnium sulfate solution while stirring rapidly. This procedure eliminated the lumpy condition but required large amounts of water; as for example four to five liters as compared to approximately one liter which was used when the mixture of dry ingredients was dissolved in water. Accordl0 ingly, the method of employing hot solutions of Ezample 4 In preparing these compositions from crude commercial materials the following composition is typical. A mixture of the following ingredien was prepared, a I

Pebble rock containing 25% Ca (Pom.--

Sulphuric mid 93% pure containing 25% wa er grams.. 453 Bauxite containing 50% A1203 -do 204 Water PP 200 After the materials had reacted, the mixture was allowed to stand and the insoluble material which settled out was removed and discarded. About four hundred twenty-six grams of tacky material were recovered which analyzed as follows,

CaO 1.00 M 0.5 A1203 18.00 F820: 3.00 P04 48.00 S04 30.00 NO: 00.03 TiOz 00.10 V205 00.05 S10: 00.10 M 00.05

Allowing for water and impurities, it is calculated that the percentage recovery of the main ingredients is as follows,

Per cent recovery Iron and aluminum 50 Sulphate 18 Phosphate 60 These recoveries may be readily further improved. The low sulphate recovery is due to the fact that the greater proportion of acid reacts with the lime to form insoluble sulphates which are removed with' other insoluble matter.

A further and very satisfactory method of preparing the compositions of this group was carried out by mixing the aluminum sulfate and di-basic calcium phosphate in a dry state in a ball mill. The finely divided homogeneous dry mixture was then exposed to live steam for a few minutes. The moisture and heat of the ingredients were dissolved separately in water 75 steam promoted the reaction and brought about tliaminel...

a tacky, sticky condition in the mass. The mass?) of silica phosphate may form. For example, such is then cooled and solidified and may be shipped; reactions may take place when magnesium in a highly concentrated form. A viscous tacky}. silicate (serpentine), readily reacting aluminum binder solution may be formed from this product{ s-Lcates such as clays hydrated silica (opal) or merely by dissolving it in water. diatomaceous e are present.

\ When the binders of this group are intended; 'llie basic or acidic phosphates, meta phoso undergo calcination, the above methods may Dhates or pyrophosphates may be used and their e modified by introducing either the phosphate degree of acidity may be modified by the addior other acid radical in the form of an ammonium tion of SUIDIIWWIE salt. During calcination this salt is decomposed, l acids, before reagtip n gl ith a umjmw leaving as the residue the stable components of 0 er met alli c su lp ha te.

the bond. I sbeen ascertained that in place of hy- The materials of this class are especially applidrated aluminum sulfate, hydrated salts in gencable in bonding, wood fiber, minwter such eral may be employed which are capable of disas feldspar and bestgs as well as in modifying solving in their own water of crystallization and the pmffllesfi cliiys. The binder is neutral in solution will react with other compounds to enough to Prevent the destruction of chrysotile form a temporarily plastic or fiuid substance by acid decomposition and by a simple drying which further reacts and solidifies to form water operation a well bonded, water resistant product resistant and insoluble materials. For examp may be obtained from this asbestos. As a variavarious other salts may be employed such as tion the binder may be produced in place by mixierrigslilfataaaluminummhlmidelierrlg chloride,

ing the ingredients with the material to be bonded magrgsiwwggp s ium ghlonde gnd and subsequently steaming or otherwise heating zin sulfate. Theswltsqnay unded the entire composition under pressure. MO! Other Substances which will For example, different binders prepared from react to form insoluble sulfates or chlorides such different molecular ratios of aluminum sulfate :15 o y- There 15 no particular limiteand calcium acid phosph atgyere sprayed on tion on the temperature at which the foregoing .r n e 1 t wa th n olded into reactions are carried out since, as has been prebriquettes under a pressure of ten thousand viously pointed out, the phosphates are stable at 1 pounds per square inch and heated in an oven to quite g temperatures- Ordinarily t e 250 C. A firm well bonded product was obtained, tion is conducted under pressures of about 10,000 i In some cases a waterproofing agent such as red p n p Square inch n et t r r s lead was mixed and ball milled with the dry asbesn in from th liq yin p int of aluminum tos. A typical composition employed in bonding sulfate (85 C.) to about 250 C. If conditions asbestos in the foregoing manner appears as require t q ying temp r t re y be follows, duced by the introduction of steam or a minor amsooaw rno grams 603 Pmmrmn water- ?lp. Example 5 f" Water on 500 40 A test of the binder in bonding asbestos was The investigation of the foregoing type of bond carried out as follows. The following dry mixprovided'an even broader concept of the compositure was ball milled.

tions falling within this group. It has been de- Per cent by weight termined that certain metallic salts of inorganic Asbestos 30 acids exist as ydrat s in whi t d e of 5 Aluminum sulfate and calcium phosphate hydration is sufilcient to dissolve and liquefy the Barium carbonate 20 salt under certain conditions of temperature and pressure at which the water of crystallization is released from the crystal lattice. The metallic salts thus dissolved in their own water of crystalli- 50 zation will react with the phosphatic material 1' 1 g gg s s g g fi g a f gg g 3,322. ingredients such as finely ground phosphate rock,

metallic salts dissolve vary with the degree of copper ferrite magnesium oxide fly ashvie 1c mod 2' ide Portland cement, talc an hydration. For example, aluminum sulfate con-- 50 mf af ball milled mixture is taining 18 mols. of water will melt in its own H o thereupon heated and pressed to liquefy the hywater or crystallization at 85 and in this form drated salt and carry out the reaction whereby g2 1rleact with calcium phosphate to produce an a water insoluble binderis formei e ent binder. By adding such basic materials Another binder composition which has been assassin:assistants; to be by soluble sulfates it is possible to obtain fully mixing equimolecular quantities of aluminum sulphate and the mono calcium phosphate as follows.

pared in molar ratio or 603 grams of sulfate con-- taining 14.5 mols. of water and 272 grams of' phosphate. To this mixture may be added barium carbonate, lead oxide or other modifying soluble reaction products as well as assist in the The mixture of sulfate and phosphate was pre-.

process of hardening or setting of the phosphate by the formation of city-phosphate. This was 05 A1 (S0 0 Parts by 2;; verified by experimental work in bonding asbestos 1 5 "T", 252

with a mixture of a hydrated aluminum sulfate, 4

a calcium -u; n u u r dicalci I In the above binders the mono and di-calcium phosphate or calcium meta phosphate an an Phosphates y be replaced by the suP D insolubllizer for the sulfate radical such as Dhetes for example t p p rp q p atebarium carbonate or lead oxide. Upon applying V heat and pressure. the hydrated salt liquefied TYPE Iv and the reaction took place forming a non-porous The compositions comprising this group represtrong bond. In the presence of readily decomsent a further modification of the method of posed silicates or hydrated silica a certain amount preparing binders of a neutral character as setpositions herein comprise colloidal alumin forth in the two preceding groups. The comisfactorily as a bind@ The compositions of this group are primarily directed to the use arsenates in place of hosp and are of great importance.

The ready reduction of the arsenates at relato binding in the sense that they may be used only to bond or c les into a coher xperiments indicate manner weet each of the following requirements for comtively low temperatures and the formation of arsenous oxide during calcination which is accompanied by volatilization of the acid radical in many instances leaves a pure or almost pure oxide bond. In contrast to the phosphatic type of binders in which reduction takes place only at temperatures above 1300 C. and under severe reducing conditions the reduction of the arsenates is accomplished at relatively moderate temperatures. These binders are adapted for use in specialized fields where a pure oxide bond is desirable as in the case of bonding catalyst masses.

The raw material sources for the commercial preparation of the foregoing types of binders comprise the large phosphate rock, sulphur and bauxite deposits in this country. Thus the most direct and simple approach to the preparation of the compositions herein comprising the treatment of phosphate rock concentrate and bauxite with sulphuric acid is assured. The utilization of aluminum and iron phosphate and arsenate minerals as raw materials such as lazulite, wavellite, variscite, scorodite, dufrenite and strengite may be of interest though these minerals are not available at present in commercial quantities. Hembrock clay, which is the residue from the production of Florida phosphate rock, contains some wavellite. However, this is so finely divided and so intimately mixed with the clay that it is dimcult to separate it by flotation or other commercial separating methods. Leaching with acid or sulphate, chloride or nitratesolutions followed by sedimentation and washing of the solid residue may prove to be a feasible method for extracting the aluminum phosphate values in this residue. A cheap source of iron sulfate is the waste pickling liquor. j

The compositions herein considered have been directed to the trivalent metal phosphates and the di and mono-valent metal phosphates have not been discussed. These latter phosphatic materials form tacky solutions in certain instances such as zinc phosphate in phosphoric acid. The efllcacy of these materials is less definite and their principal application resides merely in their use as modifying agents for the trivalent metal phosphate solutions. 11/? The binder compositions disclosed herein ercial binders or cements,

1. They are available in liquid as well as solid form.

2. The solid form permits ready transformation into the liquid form by the addition or water or other suitable solvent.

3. The binder in liquid state does not form dilatant muds with minerals such as asbestos, feldspar, etc. This is in some instances the case with sodium silicate solutions.

4. The binder permits, within limits, a control of its degree of acidity,

5. It permits dilution to any desirable extent without precipitation or solid matter by reaction with water and also permits concentration by heating without decomposition.

6. At a specified water content the binder has a definite viscosity and definite reproducible adhesive properties. The manufacturing process is simple and flexible.

I claim:

A method oi preparing a mineral binder comprising forming a homogeneous dry mixture of aluminum sulphate capable oi liquefying in its 'l "applicable in the adsorbent field. They may g ;employed to bond such adsorbents as bauxite on, *aluminum hydrate, fullers earth, activated carbon, silica gel. magnesium oxide and magnesium silicate. However, their uses are not limited solely water of crystallization calcium phosphate and an insolubilizing basic compound selected from the group consisting of barium carbonate and lead oxide capable of reacting with the metal salt in a molten condition and thereafter submitting the dry mixture to heat and pressure to liquei'y the aluminum sulphate and react the calcium phosphate and insolubilizing compound therewit HERBERT H. GREGER.

REFERENCES CITED The following references are oi. record in the file of this patent:

UNITED STATES PATENTS Number Name Date 771,184 Steenbock Sept. 27, 1904 923,238 Ames June 1, 1909 1,081,573 Boeck Dec, 16, 1913 1,310,901 Andresen July 22, 1919 1,578,812 Dawes et al Mar. 30, 1926 1,886,982 Simon Nov. 8, 1932 2,007,052 Howe July 2, 1935 2,035,140 Bri11. Mar. 24, 1936 FOREIGN PATENTS Number Country Date 4,954 Great Britain 1883 8,314 Great Britain 1896 233,907 Great Britain May 21, 1925 521,694 Great Britain May 29, 1940 

